由六氟丙酮三水合物和苯胺,经缩合、重氮化、水解、Friedel-Crafts烷基化4步反应常压下合成了双酚AF. 以五氧化二铌为催化剂,在n(HFA·3H_2O):n(aniline):n(Nb_2O_5)=2:1:0.1,回流6 h条件下,合成出中间体(Ⅰ),收率高达96.3%. 重氮化温度为-2～2 ℃、H_2SO_4质量分数为14.7%、n(Ⅰ):n(H_2SO_4):n(NaNO_2)=1:4.1:1.1、及水解时H_2SO_4质量分数为 50%、n(H_2SO_4):n(Ⅰ)=11.0:1、108～112 ℃反应1.5～2 h的优化条件下,化合物Ⅰ经重氮化、水解后以92.7%的高收率得到中间体2-(4-羟基苯)六氟异丙醇(Ⅱ);再在甲磺酸存在下,化合物Ⅱ与苯酚经Friedel-Crafts烷基化反应以72.4% 的收率合成了目标产物双酚 AF(Ⅲ),总收率为64.6%(以苯胺为基准计算).
Bisphenol AF was prepared from HFA o 3H_2O and aniline under atmospheric pressure in 4 steps; condensation, diazotization, hydrolysis and Friedel-Crafts alkylation. Firstly, 2-(4-aminophenyl)-1, 1,1,3 , 3,3-hexafluoropropan-2-ol( Ⅰ ) was obtained in a yield of 96. 3% from HFAo3H_2O and aniline under optimal conditions with Nb_2O_5 as catalyst at an n( HFA o3H_2O):n( aniline): n( Nb_2O_5 ) ratio of 2:1:0. 1 under reflux for 6 h. Then 2-(4-hydroxy phenyl)-1, 1, 1, 3, 3 , 3-hexafluoropropan-2-ol (Ⅱ) was synthesized from compound( Ⅰ ) via diazotization, hydrolysis. The optimum reaction conditions were as follows; during diazotization, n( Ⅰ ) :n( H_2SO_4) : n( NaNO_2) was 1:4. 1:1. 1, the mass fraction of H_2SO_4 was 14.7% and reaction temperature -2 ～2℃; during hydrolysis, the mass fraction of H_2SO_4 was 50% , n( H_2SO_4):n( Ⅰ ) is 11:1. Under these conditions, the yield was 92.7%. Subsequently, in the presence of methanesulfonic acid, the Friedel-Crafts alkylation of compound Ⅱ with phenol yielded target compound bisphenol AF( Ⅲ ) in a yield of 72. 4% . The total yield was 64. 6% based on aniline.
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